CN105247002B - Pressure sensitive adhesive composition - Google Patents
Pressure sensitive adhesive composition Download PDFInfo
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- CN105247002B CN105247002B CN201380060240.4A CN201380060240A CN105247002B CN 105247002 B CN105247002 B CN 105247002B CN 201380060240 A CN201380060240 A CN 201380060240A CN 105247002 B CN105247002 B CN 105247002B
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- acrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
A kind of pressure sensitive adhesive composition of the water resistance and adhesion property with enhancing is disclosed, said composition includes 70 99wt% acrylic polymer dispersion and 1 30wt% polyolefin dispersion.The acrylic polymer dispersion includes (1) one or more acrylate or (methyl) acrylate, (2) one or more hydrocarbon monomers, (3) one or more ethylenically unsaturated carboxylic acids, (4) one or more nitriles of (one or more) ethylenically unsaturated carboxylic acids or one or more acid amides, (5) one or more vinyl esters of (one or more) carboxylic acid, optionally (6) one or more nitrogenous acetoacetoxy-functionalized compounds, optionally (7) one or more amine-thiol chain transfer agents, and the polyolefin dispersion includes one or more polyolefin, it or can not can include acid functionality.
Description
Invention field
The present invention relates to the pressure sensitive adhesives of the water resistance with enhancing and adhesion property (PSA).Specifically, the present invention relates to
And acrylic emulsions PSA, it has the shear strength of enhancing, maintains low energy surface such as polyethylene or poly-
Good tack on propylene, without using tackifier dispersion.
Background of invention
Acrylic PSA be used to flexible material is attached on surface in many applications, and be used for such as glue
In band and label industry, this is attributed to the highly filled of them, low content of volatile organic compounds, good UV/ heat endurances
With high coating speed.Traditional acrylic emulsions have been mixed into tackifier dispersion to strengthen them on low energy surface
Tack.But there is poor water resistance using such tackifier, turn yellow, and the shortcomings that adhesion strength reduction.
Acrylic PSA is typically by emulsion or polymerisation in solution to produce, and emulsion polymerization is preferable.
Acrylic emulsions PSA adhesion property is influenceed by the type and relative quantity of monomer used in polymerization.
Therefore, it is necessary to which such acrylic emulsions PSA, it has the shear strength of enhancing, maintains low energy
Good tack on scale face such as polyethylene or polypropylene, without using tackifier dispersion.
The content of the invention
In one embodiment, there is provided be pressure sensitive adhesive composition, it includes about 70-99wt% acrylic acid
The polyolefin dispersion of compound dispersion of birdsing of the same feather flock together and about 1-30wt%, weight of the wt% based on said composition, here this third
Alkene acids polymers dispersion includes (1) one or more acrylate or (methyl) acrylate, (2) one or more hydrocarbon
Monomer, (3) one or more ethylenically unsaturated carboxylic acids, one or more nitriles of (4) (one or more) ethylenically unsaturated carboxylic acids
Or one or more acid amides, optionally one or more vinyl esters of (5) (one or more) carboxylic acid, (6) are a kind of or more
The nitrogenous acetoacetoxy-functionalized compound of kind, and optionally (7) one or more amine-thiol chain transfer agents, and this is poly- here
Olefin disperse body includes one or more polyolefin, and it or can not include acid functionality.
In an alternate embodiment, there is provided be pressure sensitive adhesive composition, it includes the third of about 70-99wt%
Alkene acids polymers dispersion and about 1-30wt% polyolefin dispersion, weight of the wt% based on said composition, here
The acrylic polymer dispersion includes (1) about 75- about 95wt% one or more acrylic acid C1-C17Arrcostab or
Person's alkyl methacrylate, it is selected from methyl acrylate, methyl methacrylate, ethyl acrylate, EMA,
Isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-BMA, isobutyl acrylate, methyl
Isobutyl acrylate, tert-butyl acrylate, Tert-butyl Methacrylate, Hexyl 2-propenoate, hexyl methacrylate, acrylic acid second
The own ester of base, ethylhexyl methacrylate, the dimethyl butyl ester of methacrylic acid 3,3, lauryl acrylate and combinations thereof or son
Group, (2) about 5- about 10wt% one or more hydrocarbon monomers, it is selected from styrene, the styrene and Alpha-Methyl benzene of carboxylation
Ethene, ethene, propylene, butylene, conjugated diene (such as copolymer of butadiene, isoprene, and butadiene and isoprene),
And combinations thereof or subgroup, (3) about 0.5- about 3wt% one or more ethylenically unsaturated carboxylic acids, it is selected from acrylic acid,
Methacrylic acid, ethylacrylic acid, crotonic acid, carboxy ethyl acrylate, maleic acid, fumaric acid, itaconic acid, citraconic acid, aconitic acid,
The derivative (such as α-chloroacrylic acid) of their halogen substitution, and these sour acid anhydrides (such as maleic anhydride and citraconic acid
Acid anhydride), and combinations thereof or subgroup, one kind of (4) about 0.5- about 5wt% (one or more) ethylenically unsaturated carboxylic acids or
A variety of nitriles, it is selected from acrylonitrile, α-chloro-acrylonitrile, methacrylonitrile and combinations thereof or subgroup, and (5) about 0.5- is about
20wt% (one or more) C2-C12One or more vinyl esters of carboxylic acid, and combinations thereof or subgroup, optionally (6)
0- about 5wt% one or more nitrogenous acetoacetoxy-functionalized compounds, and optionally (7) 0- about 0.5wt%
One or more amine-thiol chain transfer agents, gross weights of the wt% based on component 1-5, and the polyolefin dispersion here here
Comprising one or more polyolefin, it or can not include acid functionality.
In an alternate embodiment, there is provided be pressure sensitive adhesive composition, it includes 70-99wt% acrylic acid
Compound dispersion of birdsing of the same feather flock together and 1-30wt% polyolefin dispersion, weight of the wt% based on said composition, the here acrylic acid
Compound dispersion of birdsing of the same feather flock together includes (1) about 75- about 95wt% methyl methacrylate, ethyl acrylate and acrylic acid ethyl
The combination of own ester, (2) about 5- about 10wt% styrene monomer, (3) about 0.5- about 3wt% acrylic acid and propylene
The combination of sour carboxylic ethyl ester, (4) about 0.5- about 5wt% acrylonitrile, (5) about 0.5- about 20wt%'s is (a kind of or more
Kind) C9Or C10One or more nitrogenous second of one or more vinyl esters of carboxylic acid, optionally (6) 0- about 5wt%
Acyl acetoxyl group functional compound, and optionally (7) 0- about 0.5wt% one or more amine-thiol chain transfer agents, here should
Gross weights of the wt% based on component 1-5, and the polyolefin dispersion includes one or more gathering with acid functionality here
Alkene, such as ethylene-acrylic acid copolymer or propylene acrylic acid copolymer.
In an alternate embodiment, there is provided be the method for preparing pressure sensitive adhesive composition, it includes following step
Suddenly：About 70-99wt% acrylic polymer dispersion is combined with about 1-30wt% polyolefin dispersion, should
Weight of the wt% based on said composition.In the method, the acrylic polymer dispersion includes (1) one or more propylene
Acid esters or (methyl) acrylate, (2) one or more hydrocarbon monomers, (3) one or more ethylenically unsaturated carboxylic acids, (4) (one
Kind or it is a variety of) (one or more) nitrile or (one or more) acid amides of ethylenically unsaturated carboxylic acids, (5) (one or more) carboxylic
The one or more nitrogenous acetoacetoxy-functionalized compounds of one or more vinyl esters of acid, optionally (6), and optionally
Ground (7) one or more amine-thiol chain transfer agents, and the polyolefin dispersion includes one or more polyolefin, its can or
Acid functionality can not be included.
Embodiment
The present invention provides PSA composition.In particular it relates to PSA composition, it contains 70-99wt% propylene
(containing one or more polyolefin, it can or can be with for acids polymers dispersion and 1-30wt% polyolefin dispersion
Do not include acid functionality), weight of the wt% based on said composition.
Acrylic polymer dispersion
The PSA composition of the present invention includes 70-99wt% acrylic polymer dispersion, its include (1) one kind or
A variety of acrylate or (methyl) acrylate, (2) one or more hydrocarbon monomers, (3) one or more olefinic unsaturation carboxylics
Acid, one or more nitriles or one or more acid amides of (4) (one or more) ethylenically unsaturated carboxylic acids, (5) are (a kind of or more
Kind) one or more vinyl esters of carboxylic acid, optionally (6) one or more nitrogenous acetoacetoxy-functionalized compounds,
Optionally (7) one or more amine-thiol chain transfer agents.
(1) example for the acrylate or methacrylate for being applied to the present invention includes acrylic acid C1-C17Arrcostab
Or alkyl methacrylate.Typical example includes methyl acrylate, methyl methacrylate, ethyl acrylate, methyl
Ethyl acrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-BMA, acrylic acid
Isobutyl ester, Isobutyl methacrylate, tert-butyl acrylate, Tert-butyl Methacrylate, Hexyl 2-propenoate, methacrylic acid oneself
Ester ethylhexyl acrylate, ethylhexyl methacrylate, the dimethyl butyl ester of methacrylic acid 3,3, lauryl acrylate and its
Any combination or subgroup.
The PSA composition of the present invention can include about 75- about 95wt% acrylate or (methyl) acrylic acid
Ester, the weight based on component 1-5.
(2) being applied to the example of the hydrocarbon monomer of the present invention includes distyryl compound (such as styrene, the styrene of carboxylation
And α-methylstyrene), ethene, propylene, butylene and conjugated diene (such as butadiene, isoprene, and butadiene and isoamyl two
The copolymer of alkene) and its any combination or subgroup.
The PSA composition of the present invention can include about 5- about 10wt% hydrocarbon monomer, the weight based on component 1-5.
(3) example of ethylenically unsaturated carboxylic acids includes monoethylenically unsaturated monocarboxylic such as acrylic acid, methacrylic acid, second
Base acrylic acid, crotonic acid and carboxy ethyl acrylate, monoethylenically unsaturated dicarboxylic acid such as maleic acid, fumaric acid, itaconic acid and lemon
Health acid, monoene belong to unsaturated tricarboxylic acids such as aconitic acid, and its derivative (such as α-chloroacrylic acid) of halogen substitution and these
The acid anhydrides (such as maleic anhydride and citraconic anhydride) of acid.
The PSA composition of the present invention can include about 0.5- about 3wt% monoethylenically unsaturated carboxylic acid, based on component
1-5 weight.
(4) example of the nitrile of ethylenically unsaturated carboxylic acids above includes acrylonitrile, α-chloro-acrylonitrile and methacrylonitrile.This
The example of the acid amides of a little carboxylic acids includes unsubstituted acid amides such as (methyl) acrylamide and the acrylamide and n- of other α substitutions
Substituted acid amides, it is to be reacted by the acid amides of aforementioned carboxylic acid with aldehyde (such as formaldehyde) to obtain.The acyl of typical n- substitutions
Amine includes n- NMAs, the n- NMAs of n- methylol methacrylamides alkylation, and n- hydroxyl first
Butylmethacrylamide (such as n- methoxies acrylamide and n- methoxy methyls butylmethacrylamide).
The present invention PSA composition can comprising about 0.5- about 5wt% monoethylenically unsaturated carboxylic acid nitrile and/or
Acid amides, the weight based on component 1-5.
(5) being applied to the example of the vinyl esters of the carboxylic acid of the present invention includes C2-C12The vinyl esters of carboxylic acid, such as carboxylic acid
VeoVaTM9 vinyl esters or VeoVaTM10 vinyl esters, the two city are sold by Momentive Specialty
Chemicals Inc。
The PSA composition of the present invention can include the vinyl esters of about 0.5- about 6wt% carboxylic acid, based on component 1-
5 weight.
(6) when deployed, suitable for the example of the optional nitrogenous acetoacetoxy-functionalized compound of the invention
Include the t-butylaminoethyl methacrylate of one or more, dimethylaminoethyl methacrylate, methacrylic acid
The amino ethyl ester of diethyl -5, N, N- dimethylaminopropyl Methacrylamides, methacrylic acid 2- t-butylaminoethyls, third
Olefin(e) acid N, N- dimethylamino ethyl ester, N- (2- methacrylamidos-ethyl) ethylene ureas and N- (2- methacryloxypropyl second
Base) ethylene urea.N- (2- methylacryoyloxyethyls) ethylene urea is as 25% solution in methyl methacrylate, in business
Obtained from EvonikCyro LLC's under entitling Rohamere 6844-O.
When deployed, PSA composition of the invention can include about 0.5- about 5wt% nitrogenous acetoacetyl oxygen
Base functional compound, the weight based on component 1-5.
(7) when deployed, C is included suitable for the example of the optional alkyl hydrosulfide chain-transferring agent of the present invention6-C18Alkyl sulfide
Alcohol such as n- hexyl mercaptans, n- octyl mercaptans and n- lauryl mercaptans.
When deployed, PSA composition of the invention can include about 0.05- about 0.5wt% amine-thiol chain transfer agents,
Weight based on component 1-5.
In an alternate embodiment, pressure sensitive adhesive composition of the present invention there is no tackifier.
In an alternate embodiment of the present invention, the dispersion also includes continuous phase (being typically water), and can
With including this area it is conventional and known other components such as surfactant.
Polyolefin dispersion
The PSA composition of the present invention includes 1-30wt% polyolefin dispersion, and it includes one or more polyolefin, example
Such as polyethylene or polypropylene.In one embodiment, the polyolefin can include acid functionality, such as such as ethene-the third
Olefin(e) acid copolymer or propylene acrylic acid copolymer.
In one embodiment, polyolefin dispersion includes ethylene-acrylic acid copolymer, such as available commercially from
Michelman, Inc'sPrime 4990R。
The present invention is better understood from (including its representative advantages) to provide, there is provided the following examples.
Embodiment
Table 1 lists the composition of acrylic polymer dispersion and the acrylic polymer dispersion of contrast.
The acrylic polymer dispersion component of table 1
1Sipomer B-CEA are β-acryloxypropionic acid (mixtures of acrylic acid oligomer), obtained from Rhodia.
Comparative example 1
In order to prepare PSA latex compositions, pre-emulsion is formed by mixing following component：242.3g water, 45.9g gather
(oxygen -1,2- ethylidene), α-sulfonation-ω-[1- (methylol) -2- (2- propenyloxy groups) ethyoxyl] -, the C10-14- rich in C11
The ammonium salt of branched alkyl ether, 4.6g aliphatic ethoxylate nonionic surfactant (50% active material),
53.6g styrene, 53.6g ethyl acrylates, the vinyl esters of 23.0g neodecanoic acids, 597.0g 2-EHAs,
25.8g methyl methacrylates, 3.8g Sipomer B-CEA (being obtained from Rhodia), 11.5g acrylic acid, 0.95g N- (2-
Methylacryoyloxyethyl) ethylene urea and 0.92g N- lauryl mercaptans.It is prepared for the solution of two kinds of difference：(A) exist
55.1g the sodium peroxydisulfate of the 2.3g in water, and the 1.53g sodium peroxydisulfates of (B) in 13.8g water.By 257.8g water and 1.5g
SR-3025 surfactants are added in the reactor (available commercially from Adeka Corporation).Start nitrogen purging, and carry out
It is heated to 78 DEG C.At 78 DEG C, the 32g pre-emulsion is added in the reactor.Solution B is added in the kettle, and uses 3g
Water rinses.Turn off nitrogen purging, and start exothermic heat of reaction.15 minutes after exothermic peak, by the mixing from pre-emulsion groove and solution A
Logistics enters in reactor 4 hours, and the temperature of reactor is controlled at 85 DEG C.After the completion of flowing, by pre-emulsion 15g
Water is rinsed, and the reactor is kept for 45 minutes at 87 DEG C, is then cooled down.The tert-butyl hydroperoxide for being prepared for 2.2g exists
Solution (D) of the sodium formaldehyde sulfoxylate of solution (C) and 1.5g in 22.7g water in 23.3g water.At 60 DEG C, by 2.5g's
The aqueous solution of 28% ammonia is added in the reactor.Start to flow into solution C and D in reactor in 60 minutes, and should
Reactor is kept for other 15 minutes.The reactor is cooled to room temperature, and pH is adjusted to 6- with the aqueous solution of 28% ammonia
8.Then 75g Michem Prime 4990R are added in the kettle.
Embodiment 1
It is identical with comparative example 1, except monomer mixture is changed into 53.6g styrene, 53.6g ethyl acrylates, 581.7g
2-EHA, 28.2g methyl methacrylates, 15.3g acrylonitrile, the vinyl esters of 23.0g neodecanoic acids, 3.8g's
Sipomer B-CEA, 11.5g acrylic acid, 1.7g N- (2- methylacryoyloxyethyls) ethylene ureas and 0.69g n- dodecanes
Outside base mercaptan.Then 75g Michem Prime 4990R are added in the kettle.
The sample is to dry 5 minutes by being coated in 2 mil PET films, and at 110 DEG C come what is tested, and target dry is glued
It is 21g/m to tie agent coating weight2.The pet layer of the coating is pressed onto on exfoliated pad.PET/ binding agents/the gasket construction is cut
1 inch of wide bar is cut into, removes exfoliated pad, and the PET film with binding agent is laminated to stainless steel (SS) and high density
On polyethylene base material (HDPE), for 15min and 24 hour and the peel test of 7 day residence time.The shearing of the binding agent is
Apply 4-lb weight by the bottom of 2.54cm × 2.54cm bars on steel plate is adhered to determine.By this be stained with it is described
The steel plates of coated strands is kept on the top of the shelf, to cause the plate shape into 178 ° -180 ° of angle.The test-strips are recorded in 23 DEG C of wholes
Time (in hours) needed for failure is used as shear strength.As a result it is shown in table 2 below：
The performance comparision of table 2
| Embodiment 1 | Comparative example | |
| PL15SS(lbs/in) | 3.27 | 3.50 |
| PL24SS(lbs/in) | 6.68 | 3.96 |
| PL1W SS(lbs/in) | 6.5 | 4.44 |
| PL15HDPE(lbs/in) | 1.32 | 1.87 |
| PL24HDPE(lbs/in) | 1.53 | 3.84 |
| PL1W HDPE(lbs/in) | 1.96 | 4.38 |
| Shear (1x1x4lbs) hrs | 38.3 | 9.0 |
Comparative example 2：
Pre-emulsion is formed by mixing following component：242.3g water, the sulphur of 25.0g dodecyl diphenyls ether two
Sour sodium (46% active component), 4.6g aliphatic ethoxylate nonionics surfactant (50% active component), 53.6g
Styrene, 76.6g ethyl acrylates, 597.0g 2-EHAs, 27.0g methyl methacrylates, 3.8g's
Sipomer B-CEA and 7.5g acrylic acid.It is prepared for the solution of two kinds of difference：(A) in 55.1g water 2.3g sodium peroxydisulfate,
The 1.53g sodium peroxydisulfates of (B) in 13.8g water.257.8g water is added in the reactor.Nitrogen purging is proceeded by, and
It is heated to 78 DEG C.At 78 DEG C, the 32g pre-emulsion is added in the reactor.Solution B is added in the kettle, and uses 3g
Water rinses.Turn off nitrogen purging, and start exothermic heat of reaction.15 minutes after exothermic peak, by the mixing from pre-emulsion groove and solution A
Logistics enters in reactor 4 hours, and the temperature of reactor is controlled at 85 DEG C.After the completion of flowing, by pre-emulsion 15g
Water is rinsed, and the reactor is kept for 45 minutes at 87 DEG C, is then cooled down.The tert-butyl hydroperoxide for being prepared for 2.2g exists
Solution (D) of the sodium formaldehyde sulfoxylate of solution (C) and 1.5g in 22.7g water in 23.3g water.At 60 DEG C, by 2.5g's
The aqueous solution of 28% ammonia is added in the reactor.Start to flow into solution C and D in reactor in 60 minutes, and should
Reactor is kept for other 15 minutes.The reactor is cooled to room temperature, and pH is adjusted to 6- with the aqueous solution of 28% ammonia
8。
Comparative example 2a：3g dioctyl sodium sulphosuccinates and 15g Michem Prime4990R are added under mixing
In 300g comparative example 2.
Comparative example 2b：3g dioctyl sodium sulphosuccinates are added in 300g comparative example 2 under mixing.
Comparative example 3：
It is identical with comparative example 1, except monomer mixture is changed into 53.6g styrene, 76.6g ethyl acrylates, 597.0g
2-EHA, 32.2g methyl methacrylates, 3.8g Sipomer B-CEA, 7.5g acrylic acid, 1.7g N-
The n- lauryl mercaptans of (2- methylacryoyloxyethyls) ethylene urea and 0.69g.
Comparative example 3a：3g dioctyl sodium sulphosuccinates and 15g Michem Prime4990R are added under mixing
In 300g comparative example 3.
Comparative example 3b：3g dioctyl sodium sulphosuccinates are added in 300g comparative example 3 under mixing.
Embodiment 2：
It is identical with comparative example 1, except monomer mixture is become into 53.6g styrene, 53.6g ethyl acrylates, 574.0g
2-EHA, 32.2g methyl methacrylates, 28.2g acrylonitrile, the vinyl esters of 23.0g neodecanoic acids, 3.8g's
Sipomer B-CEA, 11.5g acrylic acid, 1.7g N- (2- methylacryoyloxyethyls) ethylene ureas and 0.69g n- dodecanes
Base mercaptan.
Embodiment 2a：3g dioctyl sodium sulphosuccinates and 15g Michem Prime4990R are added under mixing
In 300g embodiment 2.
Comparative example 2b：3g dioctyl sodium sulphosuccinates and 30g Michem Prime4990R are added under mixing
In 300g embodiment 2.
Embodiment 3：
It is same as Example 2, except monomer mixture is become into 53.6g styrene, 53.6g ethyl acrylates, 489.7g
2-EHA, 28.2g methyl methacrylates, 15.3g acrylonitrile, the vinyl esters of 115.0g neodecanoic acids,
3.8g Sipomer B-CEA, 11.5g acrylic acid, 1.7g N- (2- methylacryoyloxyethyls) ethylene ureas and 0.69g N-
Lauryl mercaptan.
Embodiment 3a：3g dioctyl sodium sulphosuccinates and 15g Michem Prime4990R are added under mixing
In 300g embodiment 3.
The sample is to dry 5 minutes by being coated in 2 mil PET films, and at 110 DEG C come what is tested, and target dry is glued
It is 21g/m to tie agent coating weight2.The pet layer of the coating is pressed onto on exfoliated pad.PET/ binding agents/the gasket construction is cut
1 inch of wide bar is cut into, removes exfoliated pad, and the PET film with binding agent is laminated to stainless steel (SS) and high density
On polyethylene base material (HDPE), the peel test for 15min and 24 hour residence time.The shearing of the binding agent be by
The bottom of the 1.27cm × 1.27cm bars adhered on steel plate applies 500g weight to determine.This is stained with the coated strands
Steel plate keep on the top of the shelf, to cause the plate shape into 178 ° -180 ° of angle.The test-strips are recorded in 23 DEG C of whole failure institutes
The time (in hours) needed is used as shear strength.Two kinds of commercially available propylene from Momentive are further comprises in the test
Acids emulsion PSA：Synthebond E-2050 and 7701, for comparing.Two kinds of products all do not include acrylonitrile, neodecanoic acid
Vinyl esters, or polyolefin dispersion.Introduce the vinyl esters of acrylonitrile and neodecanoic acid and polyolefin dispersion is combined has
Help increase to HDPE tack and adhesion strength.The performance is given in Table 3 below.
The performance comparision of table 3
Claims (18)
1. a kind of pressure sensitive adhesive composition, its acrylic polymer dispersion comprising 70-99wt% and 1-30wt%'s
Polyolefin dispersion, and weight of the wt% based on said composition；
The monomer for being wherein used to prepare the acrylic polymer dispersion includes one or more acrylate or methyl-prop
Olefin(e) acid ester, one or more hydrocarbon monomers, one or more ethylenically unsaturated carboxylic acids, the one of one or more ethylenically unsaturated carboxylic acids
Kind or a variety of nitriles or one or more acid amides, and one or more vinyl esters of one or more carboxylic acids.
2. the pressure sensitive adhesive composition of claim 1, wherein the monomer bag for preparing the acrylic polymer dispersion
One or more C containing 0.5-20wt%2-C12One or more vinyl esters of carboxylic acid, and the wt% is based on the acrylic acid
The weight for compound dispersion of birdsing of the same feather flock together.
3. the pressure sensitive adhesive composition of claim 1, wherein the monomer bag for preparing the acrylic polymer dispersion
The one or more nitriles or acid amides of one or more ethylenically unsaturated carboxylic acids containing 0.5-5wt%.
4. the one or more of the pressure sensitive adhesive composition of claim 3, wherein one or more ethylenically unsaturated carboxylic acids
Nitrile or acid amides are selected from acrylonitrile, α-chloro-acrylonitrile, methacrylonitrile and (methyl) acrylamide.
5. the pressure sensitive adhesive composition of claim 1, the wherein polyolefin dispersion include one or more polyolefin, it can
With or can not include acid functionality.
6. the pressure sensitive adhesive composition of claim 1, wherein the monomer bag for preparing the acrylic polymer dispersion
Contain：
I.75-95wt% one or more acrylate or methacrylate；
Ii.5-10wt% one or more hydrocarbon monomers；
Iii.0.5-3wt% one or more ethylenically unsaturated carboxylic acids；
The one or more nitriles or acid amides of iv.0.5-5wt% one or more ethylenically unsaturated carboxylic acids；
V.5-20wt% one or more vinyl esters of one or more carboxylic acids；
Vi. optional 0-5wt% t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, methyl
The amino ethyl ester of acrylic acid diethyl -5, N, N- dimethylaminopropyl Methacrylamides, methacrylic acid 2- tert-butylaminos
Ethyl ester, acrylic acid N, N- dimethylamino ethyl ester, N- (2- methacrylamidos-ethyl) ethylene ureas and N- (2- metering systems
Acyloxyethyl) one or more in ethylene urea；With
Vii. optional 0-0.5wt% one or more amine-thiol chain transfer agents；
And weight of the wt% based on component i-v, wherein the wt% sums of each component are 100wt%；
Wherein the polyolefin dispersion includes one or more polyolefin, and it may or may not include sour function
Degree.
7. the pressure sensitive adhesive composition of claim 6, wherein the monomer bag for preparing the acrylic polymer dispersion
Contain：
I. following one or more acrylate or methacrylate are selected from：Methyl acrylate, methyl methacrylate,
Ethyl acrylate, EMA, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, metering system
Sour N-butyl, isobutyl acrylate, Isobutyl methacrylate, tert-butyl acrylate, Tert-butyl Methacrylate, acrylic acid oneself
Ester, hexyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, the dimethyl butyl ester of methacrylic acid 3,3 and
Lauryl acrylate；
Ii. following one or more hydrocarbon monomers are selected from：Styrene, α-methylstyrene, ethene, propylene, butylene and conjugation two
Alkene；
Iii. following one or more ethylenically unsaturated carboxylic acids are selected from：Acrylic acid, methacrylic acid, ethylacrylic acid, crotons
Acid, carboxy ethyl acrylate, maleic acid, fumaric acid, itaconic acid, citraconic acid, aconitic acid, and spread out including what their halogen substituted
Biology and acid anhydrides；
Iv. one or more nitriles selected from following one or more ethylenically unsaturated carboxylic acids or one or more acid amides：Third
Alkene nitrile, α-chloro-acrylonitrile and methacrylonitrile；
V. one or more C2-C12One or more vinyl esters of carboxylic acid；
Vi. optional t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, methacrylic acid diethyl
The amino ethyl ester of base -5, N, N- dimethylaminopropyl Methacrylamides, methacrylic acid 2- t-butylaminoethyls, acrylic acid
N, N- dimethylamino ethyl ester, N- (2- methacrylamidos-ethyl) ethylene ureas and N- (2- methylacryoyloxyethyls) second
One or more in alkene urea；With
Vii. optional one or more amine-thiol chain transfer agents；And weight of the wt% based on component i-v；
Wherein the polyolefin dispersion, which includes one or more, includes the polyolefin of acid functionality.
8. the pressure sensitive adhesive composition of claim 6, wherein the monomer bag for preparing the acrylic polymer dispersion
Contain：
I. the combination of methyl methacrylate, ethyl acrylate and ethylhexyl acrylate；
Ii. styrene；
Iii. the combination of acrylic acid and carboxy ethyl acrylate；
Iv. acrylonitrile；
V. one or more vinyl esters of one or more C9 or C10 carboxylic acids；
Vi.0.5-5wt% t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, metering system
The sour amino ethyl ester of diethyl -5, N, N- dimethylaminopropyl Methacrylamides, methacrylic acid 2- t-butylaminoethyls,
Acrylic acid N, N- dimethylamino ethyl ester, N- (2- methacrylamidos-ethyl) ethylene ureas and N- (2- methacryloxypropyl second
Base) one or more in ethylene urea；With
Vii.0.05-0.5wt% one or more amine-thiol chain transfer agents；Weight of the wt% based on component i-v；
Wherein the polyolefin dispersion, which includes one or more, includes the polyolefin of acid functionality, and it is selected from ethylene-acrylic acid
Copolymer and propylene acrylic acid copolymer.
9. the pressure sensitive adhesives of claim 6, wherein one or more amine-thiol chain transfer agents are C6-C18 alkyl hydrosulfides.
10. a kind of method for manufacturing pressure sensitive adhesive composition, it includes：
70-99wt% acrylic polymer dispersion is combined with 1-30wt% polyolefin dispersion, the wt% is based on
The weight of said composition；
Wherein it is used to prepare one or more second that the monomer of the acrylic polymer dispersion includes one or more carboxylic acids
Alkenyl esters, and one or more nitriles of one or more ethylenically unsaturated carboxylic acids or one or more acid amides.
11. the method for claim 10, wherein including 0.5- for the monomer for preparing the acrylic polymer dispersion
20wt% one or more C2-C12One or more vinyl esters of carboxylic acid, the wt% is based on the acrylic polymer point
The weight of granular media.
12. the method for claim 10, wherein including 0.5-5wt% for the monomer for preparing the acrylic polymer dispersion
One or more ethylenically unsaturated carboxylic acids one or more nitriles or acid amides.
13. the one or more nitriles or one kind of the method for claim 12, wherein one or more ethylenically unsaturated carboxylic acids
Or a variety of acid amides are selected from acrylonitrile, α-chloro-acrylonitrile, methacrylonitrile and (methyl) acrylamide.
14. the method for claim 10, the wherein polyolefin dispersion include one or more polyolefin, it can or can be with
Do not include acid functionality.
15. the method for claim 10, wherein being included for the monomer for preparing the acrylic polymer dispersion：
I.75-95wt% one or more acrylate or methacrylate；
Ii.5-10wt% one or more hydrocarbon monomers；
Iii.0.5-3wt% one or more ethylenically unsaturated carboxylic acids；
The one or more nitriles or one or more acid amides of iv.0.5-5wt% one or more ethylenically unsaturated carboxylic acids；
V.5-20wt% one or more vinyl esters of one or more carboxylic acids；
Vi. optional 0-5wt% one or more nitrogenous acetoacetoxy-functionalized compounds；With
Vii. optional 0-0.5wt% one or more amine-thiol chain transfer agents；
Weight of the wt% based on component i-v, wherein the wt% sums of each component are 100wt%；
Wherein the polyolefin dispersion includes one or more polyolefin, and it may or may not include sour function
Degree.
16. the method for claim 15, wherein being included for the monomer for preparing the acrylic polymer dispersion：
I. following one or more acrylate or methacrylate are selected from：Methyl acrylate, methyl methacrylate,
Ethyl acrylate, EMA, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, metering system
Sour N-butyl, isobutyl acrylate, Isobutyl methacrylate, tert-butyl acrylate, Tert-butyl Methacrylate, acrylic acid oneself
Ester, hexyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, the dimethyl butyl ester of methacrylic acid 3,3 and
Lauryl acrylate；
Ii. following one or more hydrocarbon monomers are selected from：Styrene, α-methylstyrene, ethene, propylene, butylene and conjugation two
Alkene；
Iii. following one or more ethylenically unsaturated carboxylic acids are selected from：Acrylic acid, methacrylic acid, ethylacrylic acid, crotons
Acid, carboxy ethyl acrylate, maleic acid, fumaric acid, itaconic acid, citraconic acid, aconitic acid, and the derivative substituted including their halogen
Thing and acid anhydrides；
Iv. one or more nitriles of one or more ethylenically unsaturated carboxylic acids or one or more acid amides, its be selected from acrylonitrile,
α-chloro-acrylonitrile and methacrylonitrile；
V. one or more vinyl esters of one or more C2-C12 carboxylic acids；
Vi. optional one or more nitrogenous acetoacetoxy-functionalized compounds；With
Vii. optional one or more amine-thiol chain transfer agents；Weight of the wt% based on component i-v；
Wherein the polyolefin dispersion, which includes one or more, includes the polyolefin of acid functionality.
17. the method for claim 15, wherein being included for the monomer for preparing the acrylic polymer dispersion：
I. the combination of methyl methacrylate, ethyl acrylate and ethylhexyl acrylate；
Ii. styrene；
Iii. the combination of acrylic acid and carboxy ethyl acrylate；
Iv. acrylonitrile；
V. one or more vinyl esters of one or more C9 or C10 carboxylic acids；
Vi.0.5-5wt% t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, metering system
The sour amino ethyl ester of diethyl -5, N, N- dimethylaminopropyl Methacrylamides, methacrylic acid 2- t-butylaminoethyls,
Acrylic acid N, N- dimethylamino ethyl ester, N- (2- methacrylamidos-ethyl) ethylene ureas and N- (2- methacryloxypropyl second
Base) one or more in ethylene urea；With
Vii.0.05-0.5wt% one or more amine-thiol chain transfer agents；Weight of the wt% based on component i-v；
Wherein the polyolefin dispersion, which includes one or more, includes the polyolefin of acid functionality, and it is selected from ethylene-acrylic acid
Copolymer and propylene acrylic acid copolymer.
18. the method for claim 10, wherein one or more amine-thiol chain transfer agents are C6-C18 alkyl hydrosulfides.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201261727977P | 2012-11-19 | 2012-11-19 | |
| US61/727,977 | 2012-11-19 | ||
| PCT/US2013/070575 WO2014078793A1 (en) | 2012-11-19 | 2013-11-18 | Pressure sensitive adhesive compositions |
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| Publication Number | Publication Date |
|---|---|
| CN105247002A CN105247002A (en) | 2016-01-13 |
| CN105247002B true CN105247002B (en) | 2018-02-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380060240.4A Active CN105247002B (en) | 2012-11-19 | 2013-11-18 | Pressure sensitive adhesive composition |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US9243171B2 (en) |
| EP (1) | EP2941465A4 (en) |
| KR (1) | KR101797833B1 (en) |
| CN (1) | CN105247002B (en) |
| WO (1) | WO2014078793A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11306169B2 (en) * | 2015-08-05 | 2022-04-19 | Synthomer Usa Llc | Pressure sensitive adhesive compositions and methods for preparing same |
| ES2828697T5 (en) * | 2015-08-05 | 2024-04-09 | Synthomer Usa Llc | Pressure sensitive adhesive compositions and methods for preparing them |
| CN108299658B (en) * | 2017-01-13 | 2022-07-22 | 东邦化学工业株式会社 | Aqueous dispersion |
| JP6868112B2 (en) * | 2017-02-03 | 2021-05-12 | シントマー ユーエスエイ リミテッド ライアビリティ カンパニー | Pressure-sensitive pressure-sensitive adhesive composition and method for preparing it |
| CN110582548A (en) * | 2017-03-13 | 2019-12-17 | 陶氏环球技术有限责任公司 | Water-based pressure-sensitive adhesive composition and method for producing the same |
| BR112020005228B1 (en) * | 2017-09-27 | 2023-11-28 | Rohm And Haas Company | ADHESIVE COMPOSITION, METHOD FOR PREPARING AN ADHESIVE COMPOSITION BY EMULSION POLYMERIZATION AND FOOD CONTACT ARTICLE |
| CN109400794B (en) * | 2018-09-29 | 2020-11-27 | 佛山市三水协佳化工有限公司 | Synthetic method of resin for leather edge oil |
| KR102361620B1 (en) | 2018-10-23 | 2022-02-09 | 주식회사 엘지화학 | Electrode binder composition for rechargeable battery and electrode mixture including the same |
| KR102267592B1 (en) * | 2018-11-02 | 2021-06-21 | 주식회사 엘지화학 | Preparation method of aqueous adhesive composition for clothes |
| WO2020091467A1 (en) * | 2018-11-02 | 2020-05-07 | 주식회사 엘지화학 | Method for manufacturing aqueous adhesive for clothing |
| EP3653681A1 (en) * | 2018-11-15 | 2020-05-20 | Arkema France | Pressure-sensitive adhesive compositions and related aqueous polymer dispersions |
| KR102262503B1 (en) | 2018-12-17 | 2021-06-08 | 주식회사 엘지화학 | Preparation method of acrylic emusion resin |
| AR123472A1 (en) * | 2020-09-15 | 2022-12-07 | Dow Global Technologies Llc | ACRYLIC-BASED ADHESIVE COMPOSITION WITH ETHYLENE-BASED POLYMER |
| CN115881968A (en) * | 2023-01-18 | 2023-03-31 | 深圳好电科技有限公司 | Non-fluorine positive electrode adhesive and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3919153A (en) * | 1966-04-06 | 1975-11-11 | United Merchants & Mfg | Adhesive compositions |
| CA1318427C (en) * | 1986-09-09 | 1993-05-25 | Glenn R. Frazee | Aqueous pressure sensitive adhesive compositions |
| US4879333A (en) | 1986-09-09 | 1989-11-07 | S. C. Johnson & Son, Inc. | Aqueous pressure sensitive adhesive compositions |
| US5049608A (en) * | 1989-05-03 | 1991-09-17 | Air Products And Chemicals, Inc. | Acrylic pressure sensitive adhesive compositions having improved low temperature adhesion |
| KR960003285B1 (en) * | 1991-07-18 | 1996-03-08 | 미쓰이도오아쓰 가가쿠 가부시키가이샤 | Resin composition |
| US5486426A (en) * | 1993-10-04 | 1996-01-23 | Mobil Oil Corporation | Cold sealable cohesive polymer coated polyolefin substrate |
| DE60134754D1 (en) * | 2001-12-07 | 2008-08-21 | 3M Innovative Properties Co | Acrylic pressure sensitive hot melt adhesive and its use |
| US6927267B1 (en) * | 2002-03-07 | 2005-08-09 | Basf Ag | High solids dispersion for wide temperature, pressure sensitive adhesive applications |
| JP2010515794A (en) * | 2007-01-12 | 2010-05-13 | サイテック サーフェース スペシャリティーズ、エス．エイ． | Polymer compositions and methods |
| WO2008111663A1 (en) * | 2007-03-13 | 2008-09-18 | Lintec Corporation | Pressure sensitive adhesive film for wheel bonding |
| CN101147739B (en) * | 2007-07-06 | 2010-12-08 | 北京康倍得医药技术开发有限公司 | Composition containing rotigotine and its use and transdermal patch containing the composition |
| JP5725760B2 (en) * | 2010-08-19 | 2015-05-27 | 大同化成工業株式会社 | Acrylic polymer compounds used in pressure-sensitive adhesive compositions for touch panels |
| JP5941906B2 (en) * | 2011-03-24 | 2016-06-29 | リンテック株式会社 | Adhesive composition and adhesive sheet |
| US10160891B2 (en) * | 2012-02-08 | 2018-12-25 | Honeywell International Inc. | High performance water-based tackified acrylic pressure sensitive adhesives |
-
2013
- 2013-11-18 CN CN201380060240.4A patent/CN105247002B/en active Active
- 2013-11-18 EP EP13855374.8A patent/EP2941465A4/en not_active Withdrawn
- 2013-11-18 US US14/082,776 patent/US9243171B2/en active Active
- 2013-11-18 KR KR1020157016504A patent/KR101797833B1/en active IP Right Grant
- 2013-11-18 WO PCT/US2013/070575 patent/WO2014078793A1/en active Application Filing
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| US20140142238A1 (en) | 2014-05-22 |
| EP2941465A4 (en) | 2016-06-01 |
| US9243171B2 (en) | 2016-01-26 |
| WO2014078793A1 (en) | 2014-05-22 |
| KR101797833B1 (en) | 2017-11-15 |
| CN105247002A (en) | 2016-01-13 |
| KR20150100684A (en) | 2015-09-02 |
| EP2941465A1 (en) | 2015-11-11 |
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